Compositions with a base of phosphoric esters combined with a stabiliser

ABSTRACT

Pesticidal compositions containing at least one phosphoric ester insecticide of which the molecule has at least one alkyl group of one to three carbon atoms, an agent for stabilising the said ester against decomposition by protonisation and used in an amount of 0.2 to 10% based on the weight of phosphoric ester, characterised in that the stabilising agent contains at least one compound selected from the compounds of the chemical class of 1,3-benzodioxoles and optionally in addition to it a further compound selected from elemental sulphur, from a divalent sulphur compound and from a diazene. Process for stabilising a phosphoric ester pesticide, the molecule of which has at least one alkyl group containing one to three carbon atoms, characterised in that there is added to the phosphoric ester or to the mixture containing it 0.2 to 10%, calculated on the weight of phosphoric ester, of an agent capable of stabilising the phosphoric ester against protonisation and being constituted by at least one compound chosen from the chemical class of benzodioxoles.

white tates Hennart et a1.

cc. 3, I974 COMPOSITIONS WITH A BASE OF PHOSPHORIC ESTERS COMBINED WITHA STABILISER [75] Inventors: Claude Illennart, Aubervilliers;

Marcel Louis Dulat, Poitiers, both of France [73] Assignee: Ciba-GeigyAG, Basie, Switzerland [22] Filed: Sept. 14, 1971 [21] Appl. No.:180,507

[30] Foreign Application Priority Data Sept. 11, 1970 France 70.33013[52] U.S. Cl. 424/219 [51] Int. Cl A0ln 9/36 [58} Field of Search424/219 [56] References Cited UNITED STATES PATENTS 2,493,927 1/1950Prill 424/278 2,826,530 3/1958 Eddy et all... 424/278 2,891,889 6/1959Haynes 424/278 2,904,463 9/1959 Moorefield .l 424/278 3,053,729 9/1962SIIII 42412 78 3,093,536 6/1963 Loeffler 424/219 3,097,128 7/1963Sprinkle et a1 424/219 3,116,201 12/1963 Whetstone 424 21 9 OTHERPUBLICATIONS Hoffman et al. J. Econ. Entomol. 47:72-76 (1954)..

Cole et a1. .1. Econ. Entomol. 492747-750 (1956). Sun et al. J. Agr.Food Chem. 8261-266 (1960). Zschintzsch Arzneimittel-Forsch 1 l:579-586,672-675 (1961), per GA.55:25l38b(l961).

Primary Examiner-Shep K. Rose Attorney, Agent, or Fz'rm-Wenderoth, Line& Ponack [57] ABSTRACT Pesticidal compositions containing at least onephosphoric ester insecticide of which the molecule has at least onealkyl group'of one to three carbon atoms, an agent for stabilising thesaid ester against decomposi tion by protonisation and used in an amountof 0.2 to 10% based on the weight of phosphoric ester, characterised inthat the stabilising agent contains at least one compound selected fromthe compounds of the chemical class of 1,3-benzodioxoles and optionallyin addition to it a further compound selected from e1emental sulphur,from a divalent sulphur compound and from a diazene.

Process for stabilising a phosphoric ester pesticide, the molecule ofwhich has at least one alkyl group containing one to three carbon atoms,characterised in that there is added to the phosphoric ester or to themixture containing it 0.2 to 10%, calculated on the weight of phosphoricester, of an agent capable of stabilising the phosphoric ester againstprotonisation and being constituted by at least one compound chosen fromthe chemical class of benzodioxoles.

6 Claims, N0 Drawings .r CQMPUSKTHQNS WITH A BASE UP PHOSPHORJM ESTERSQOMBINED WITH A STAllLlSER This invention relates to a process forstabilising pesticidal phosphoric esters, and new stabilisedcompositions containing such esters.

Phosphoric esters are now widely used as pesticides, particularly asinsecticides. Their wide use is due principally to their rapid actionand the absence of any accumulation of the compounds in living tissue asa result of their rapid hydrolysis in situ.

This last characteristic, which gives a net advantage over chlorinatedpesticides, is on the other hand, a serious disadvantage: thesensitivity of certain phosphoric acid esters to humidity, even justthat of the atmosphere, is such that decomposition takes place beforethey are able to act on the pest organisms. The esters particularlysusceptible to this are those containing low alkyl groups such asmethyl, ethyl, propyl or isopropyl attached to the phosphoric anion. Oncontact with molecules of water, at least partial decomposition of theesters takes place by protonisation, i.e. by re placement of a low alkylgroup by hydrogen.

Among the sensitive phosphoric esters, special mention should be made of-2,2-dichlorovinyl-0,0- dimethyl phosphate, better known by the commonname of DICHLORVOS or DDVP, the use of which in permanent insecticidaldevices, so-called evaporaters, has risen very greatly during recentyears.

Various methods of stabilisation have already been suggested to limitthe decomposition of there phosphoric esters, but they are generallytoxic such as phenols, amines or low nitrogen heterocyclics; anotherclass of useful stahilisers includes azoic and hydrazonic compounds, butthese possess a strong colouring ability which does not always permitthem to be used. The use of anhydrides or epoxides has also beensuggested, but it is known that these compounds act by fixation eitherof a molecule of water or of a molecule of free acid: it is clear thatthis process is stoichiometrically limited and that stabilisation ceaseswhen all stabiliser has reacted. This leads to the necessity of usingsubstantial proportions of these stahilisers, which is not economic.

It is an object of the present invention to stabilise pesticidalphosphoric esters by using substances more efficacious and not havingthe disadvantages stated above.

Certain benzodioxole derivatives have been suggested as insecticidalsynergists, i.e. as reinforcing agents for the insecticidal action oncontact with the insects, these being at very high concentrations of theorder of 200 to 500% taken on the basis of the total weight ofinsecticidal compound. it has never been found, before the presentinvention, that the benzodioxole derivatives, particularly at lowconcentrations, are useful for preserving phosphoric esters againstprotonisation.

The invention accordingly includes pesticidal compositions comprising:

A. at least one pesticidal phosphoric ester, the molecule of whichincludes at least one alkyl group of 1 to 3 carbon atoms B. an agentstabilising the ester against decomposition by protonisation and used ina proportion of 0.2 to by weight, preferably 0.5 to 6%, based on theweight of phosphoric ester, and wherein the stabiliser in the saidcomposition is chosen from 1,3- benzodioxoles. Such a composition mayoptionally contain a solvent for the phosphoric ester, which may besolid or liquid, under pressure or otherwise. It may also optionallycontain one or more inert mineral or organic adjuvants.

The present invention also includes a process for stabilising apesticidal phosphoric ester of which the molecule contains at least onealkyl group of one to three carbon atoms, optionally in admixture with asolvent for the phosphoric ester, which solvent is solid or liquid atambient temperature under pressure or not, and/or optionally inadmixture with one or more adjuvants compatible with the phosphoricester, which process comprising adding to the phosphoric ester or to amixture containing it, 0.2 to 10% calculated on the weight of phosphoricester, of an agent capable of stabilising the phosphoric ester againstprotonisation, and constituted by at least one 1,3-benzodioxole.

According to a preferred embodiment, the present invention also includescompositions comprising ingredients (A) and (B) above, and furthermoreincluding: (C) at least one second agent stabilising the said pesticidalphosphoric ester against protonisation, this second agent being selectedfrom elemental sulphur, divalent sulphur compounds such as those definedin patent application No. 180,137 filed on Sept. 13, 1971, now U.S. Pat.No. 3,836,643, and diazenes.

This second stabilising agent, used in a proportion of between 0.1 andabout 5 based on the weight of phosphoric ester pesticide, augments thestabilising effect of the principal agent in a fashion showing apronounced synergistic stabilisation action.

According to a preferred embodiment, the total proportion of stabilisingagent is between 0.5 and 6% based on the weight of phosphoric ester. Inthe proportions suggested in the present invention, the benzodioxole hasno action as toxicity synergist for the insecticidal phosphoric ester.

The preferred benzodioxoles for use in the present invention are definedby general formula I MR wherein m is l or 2, and X is an alkylene bridgeof one to seven 15 carbon atoms, an alkenylen bridge of two to sevencarbon atoms or an alkadienylene bridge of four to seven carbon atoms,and R is one of the followmg a. hydrogen b. alkyl of one to six carbonatoms unsubstituted or substituted by phenyl or nitro.

c. alkenyl of 2 to 6 carbon atoms, unsubstituted or substituted byphenyl or nitro,

d. nitro e. halogen of atomic number not greater than 35 f. low alkoxy,and A. m representing only 1 R represents one of the following informula I a. hydrogen b. low alkyl c. low alkenyl d. halogen of atomicnumber not exceeding 17 e. nitro,

f. the group in which each of R R and R independently of the others, isthe same or a different group selected from the following: hydrogen, lowalkyl, low alkoxy, hydroxy, nitro, chloro, bromo and low alkylthio:

g. the group z CH om llC-C II in which R is hydrogen or low alkyl,

h. the group /0 R W O on1 0 in which Z and Z are each independently a CCbond or an oxygen atom (0--), and R is hydrogen, low alkyl or lowalkoxy.

i. the group in which R is alkyl of one to six carbon atoms or oxaalkylof at most carbons atoms and having one or two atoms of oxygen in thechain B. m representing 1 or 2 R represents one of the followingconstituents in formula I i. cyano' ii. the group wherein R is hydrogen,low alkyl or low alkanoyl, and R is hydrogen or low alkyl,

' or R and R together with the nitrogen atom to which they are attached,constitute a pyrrolidino, piperidino. morpholino or azepino group,unsubstituted or substituted by low alkyl,

iii. the group -CO-R in which R is one of the following constituents:

a. hydrogen b. OM in which M is hydrogen or an equivalent 65 metal ion'c. low alkyl d. low alkoxy e. alkoxyalkoxy of two to seven carbon atomsf. alkoxyalkoxyalkoxy of 4 to l0 carbon atoms g. phenyl, unsubstitutedor substituted by one or more of the following substituents: low alkyl,low 5 alkoxy, chloro, bromo;

h. the group wherein each or R and R is independently selected fromhydrogen, low alkyl or phenyl iv. the group in which the alkyl group hasone to eight carbon atoms v. the group -OR in which R,; is low alkyl oroxa alkyl of at most 15 carbon atoms and three oxygen atoms in thechain.

vi. the group in d' alent s: 40 g N group 0:. the group H(IDR1OI w inwhich each of R R and R independently is hydrogen, low alkyl,alkoxycarbonyl of two to five carbon atoms, or the group COOM, M havingthe meaning given above, or

B. the group in which R is one of the following constituents,

hydrogen, low alkyl, low alkoxy, low alkanoyl or benzoyl, and Rrepresents one of the following constituents:

tween benzodioxoles having a basic function and suitwherein n is 1 or 2R is an alkylene bridge of two to four carbon atoms, and each of R and Rindependently, is hydrogen or low alkyl, or R and R taken together withthe nitrogen atom to which they are bound, are a pyrrolidino,piperidino, morpholino or azepino group.

The organic constituents noted above for formula I and qualified aboveand in what follows, and in the claims, bythe term low have at most sixcarbon atoms and preferably one to four carbon atoms.

Included also within the benzodioxoles of formula I are the more or lessvolatile addition salts formed beable organic or mineral acids. The termmetallic ion, used in defining M above, includes ammonium ions NR R R Rin which R,,,, R R and R, each independently represent hydrogen or anorganic group, chiefly low alkyl.

The term benzodioxole used in the following examples and claims alwaysmeans 1,3-benzodioxole.

Particularly preferred benzodioxoles among those defined by formula Iabove, are chosen from the following classes:

1. Simple benzodioxoles defined by formula I -R.. 1120 a o V 1 whereinR,,, is chosen from:

hydrogen, fluorine, bromine, alkyl of one to six carbon atoms,unsubstituted or substituted by nitro or phenyl, alkenyl of two to fourcarbon atoms, nitroalkenyl of two to four carbon atoms, styryl andnitro, and R,,' is chosen from:

hydrogen, fluorine, chlorine, bromine and alkyl of one to six carbonatoms.

Such compounds are, for example, the following:

a. S-nitro benzodioxole b. S-fluoro benzodioxole c. S-chlorobenzodioxole d. S-bromo benzodioxole e. 5,6-dichloro benzodioxole f.5,6-dibrorno benzodioxole g. S-methyl benzodioxole h. 5-propylbenzodioxole i. 5-isobutyl benzodioxole j. S-tertbutyl benzodioxole k.5-hexyl benzodioxole l.' S-methyl 6-propyl benzodioxole m. 5,6-dimethylbenzodioxole n. ,5-(2-nitro propyl) benzodioxole o. 5-vinyl benzodioxolep. 5-allyl benzodioxole r. 5-(propen-1-yl) benzodioxole s. S-methallylbenzodioxole t. 5-allyl 6-methyl benzodioxole u. 5-allyl 6-butylbenzodioxole v. 5-styryl benzodioxole w. 5-(2-nitro vinyl) benzodioxole6 x. 5-(2-nitro propen-l-yl) benzodioxole y. 5-benzyl benzodioxole;

2. Carbonylated benzodioxoles defined by formula II lene group, each ofwhich contains at most seven carbon atoms in straight or branched chain;R6" is hydrogen or alkyl of one to four carbon atoms or phenyloptionally substituted by one or two low alkyl groups, or a carbamoylgroup optionally substituted by one or two low alkyl groups or phenyl,and R represents hydrogen, low alkyl, chlorine, bromine, fluorine ornitro. Such compounds are, for example, the following:

a. 5-formyl benzodioxole b. 5-chloro 6-formyl benzodioxole c. S-formyl6-nitro benzodioxole d. 5-(2-formyl vinyl) benzodioxole e. S-acetylbenzodioxole f. S-acetyl 6-methyl benzodioxole g. S-propionylbenzodioxole h. S-benzoyl benzodioxole i. S-butyryl benzodioxole j.5-(2-carbamoyl ethyl) benzodioxole k. 5-(2-N-methylcarbamoyl ethyl)benzodioxole l. 5-(3-N-methylcarbamoyl propyl) benzodioxole m.S-(I-N-methylcarbamoyl 2-propyl) benzodioxole n. 5-(2-N-butylcarbamoylethyl) benzodioxole o. 5-(2-N,N-dimethylcarbamoyl ethyl) benzodioxole(2-N-phenylcarbamoyl ethyl) benzodioxole -(2-N,N-diphenylcarbamoylethyl) benzodioxole 5-(3-oxo 2-isopropyl butene-l yl) benzodioxole5-(2-benzoyl vinyl) benzodioxole k 5-(3-acetyl 2,2-diethyl propyl)benzodioxole l'. 5-(2-formyl ethyl) benzodioxole m. 5-[2-(2,4 dichlorobenzoyl) ethyl] benzodioxole n. 5 [2-(4-bromo benzoyl) ethyl]benzodioxole n. 5-(7-acetyl heptyl) benzodioxole 3. Carboxylatedbenzodioxoles defined by formula III III in which X and R,, are asdefined'in (2) above, and R is hydrogen, alkyl of one to four carbonatoms or low alkenyl, or an oxa-alkyl group containing three to sevencarbon atoms or a dioxa-alkyl group containing five to ten carbon atoms,or a phenyl group. Such compounds are, for example, the following:

a. S-carboxy benzodioxole b. S-methyoxycarbonyl benzodioxole c.S-ethoxycarbonyl benzodioxole d. 5-butoxy carbonyl benzodioxole5-(2-ethoxy ethoxy) carbonyl benzodioxole 5-(3,6-dioxa decyl)oxycarbonyl benzodioxole 5-(2-.carboxy vinyl) benzodioxole 5-(2-carboxyethyl) benzodioxole 5-(2-carboxy hepten-l yl) benzodioxole5-(2-methoxycarbonyl vinyl) benzodioxole 5- 2-butoxy carbonyl vinyl)benzodioxole 5-(2-carboxy vinyl) 6-nitro benzodioxole 5-carboxy 6-nitrobenzodioxole S-ethoxycarbonyl 6-nitro benzodioxole S-(carboxymethyl)benzodioxole 5-(4-carboxy butadien-l,3 yl) benzodioxole 5-carboxy6-chloro benzodioxole S-ethoxycarbonyl 6-methyl benzodioxoleS-phenoxycarbonyl benzodioxole S-(phenoxycarbonyl-methyl) benzodioxoleS-allyloxycarbonyl benzodioxole. 4. Nitrilated benzodioxoles defined byformula IV in which X and R are as defined in 2-) above. Such compoundsare, for example g. h. i. j. k. 5.

in which Y is a direct band or is alkylene of one to four 6 S-hydroxybenzodioxole 5-hydroxymethyl benzodioxole,

. 5-(hydroxy-2 ethyl) benzodioxole 5-(hydroxy ethyl) benzodioxole5-(3-hydroxy propyl) benzodioxole 5-( l-hydroxy propyl) benzodioxole 5-(l-hydroxy butyl) benzodioxole 6-chloro S-hydroxymethyl benzodioxoleS-hydroxy 6-methyl benzodioxole S-hydroxymethyl 6-methyl benzodioxole;

. S-hydroxy 6-bromo benzodioxole 5-(3-hydroxy butene-l yl) benzodioxole.

. Aminated benzodioxoles defined by formula VI.

0 Rd YN/ 1120 wherein R and Y are as defined in (2) and 5) aboverespectively, and R and R, are the same or different and are eachhydrogen or alkyl of one to four carbon atoms, or one of them can bealkanoyl of one to four carbon atoms, and also R and R, can represent,together with the nitrogen atom to which they are attached, pyrrolidino,piperidino,morpholino or azepino. Such compounds are, for example, thefollowing:

a. 5-(N,N-dimethylamino) benzodioxole b. 5-(N,N-dimethylaminomethyl)benzodioxole c. S-(Z-amino propyl) benzodioxole d. S-(N-formyl N-methylaminomethyl) benzodioxole S-(N-acetylaminomethyl) benzodioxole e f.-(2-N-butyrylamino propyl) benzodioxole g -(2-N-methylamino ethyl)benzodioxole h -piperidinomethyl benzodioxole l-azepinyl methyl)benzodioxole (2-morpholino ethyl) benzodioxole 5-(4-methyl piperidino)methyl benzolioxole n 5-(2-pyrrolidino ethyl) benzodioxole o.S-aminomethyl 6-nitro benzodioxole p. v5-(2-amino propyl) 6-nitrobenzodioxole q. 5-(N,N-dimethylaminomethyl) 6-nitro benzodioxole r.S-piperidino benzodioxole s. 5-(3-N,N-dimethylamino butene-l yl)benzodioxole t. S-(Z-N-methylamino ethyl) 6-isopropyl benzodioxole u.5-(2-amino propyl) 6-methyl benzodioxole v. 5-(2-arnino propyl) 6-chlorobenzodioxole.

-( 2-N,N-diethylamino butyl) benzodioxole 5 5 5 (2-N,N-dibutylaminoethyl)-benzodioxole 5 7. Benzoxazoles having a sulphoxide functiondefined I by formula VII.

Rn, v11

wherein Y is as defined in (5) above, but is preferably an alkylenebridge, R is alkyl of one to eight carbon atoms and'R is hydrogen oralkyl of one to four car- O H VIII in which Y and R are as defined inand (7) above respectively, and R is alkyl of one to four carbon atomsor alkoxyalltyl of two to seven carbon atoms, or alkoxyalkoxy-alkyl of 4to carbon atoms, or alkoxyalkoxy alkoxy alkyl of 5 to carbon atoms, orphenyl. Such compositions are, for example, the following:

a. S-methoxy benzodioxole b. 5-butoxy benzodioxole c. S-(Z-ethoxyethoxy) benzodioxole d. S-(Z-ethoxy methyl) benzodioxole e. S-(Z-methoxypropyl) benzodioxole f. 5-(2-butoxy butyl) benzodioxole g.5-(2,5,8-trioxa dodecyl) benzodioxole h. S-methyl 6-(2,5,8-trioxadodecyl) benzodioxole i. S-propyl 6-(2,5,8-trioxa dodecyl) benzodioxolej. S-butyl 6-(2,5,8-trioxa dodecyl) benzodioxole k. 6-chloroS-ethoxymethyl benzodioxole l. 5-(3-methoxy butene-l yl) benzodioxole m.S-phenoxymethyl benzodioxole n. S-ethoxy 6-nitro benzodioxole;

o. 5-(3,6, 9-trioxa undecyl-2) oxy benzodioxole p. 6-ethyl5-(3,6,9-trioxa undecyl-Z) oxy benzodioxole 9. Benzodioxoles having anacetal function defined by formula IX e. f. 5-bis(3,6-dioxadecyloxy)methyl benzodioxole Ml g. 5-bis(5-methyl 4,7-dioxadodecyloxy)methyl benzodioxole h. 5-(dipropyloxy)methyl benzodioxole i.5-(dipropyloxy)methyl 6-chloro benzodioxole j. 5-(dipropyloxy)methyl6-nitro benzodioxole k. 5-(dipropyloxy)methyl 6-methyl benzodioxole; l0.Benzodioxoles having a carbonic function defined by formula X in which Yis as defined in (5) above, and R and R are the same or different andare each hydrogen or alkyl of one to four carbon atoms, or are, togetherwith the nitrogen atoms, piperidino, morpholino or pyrrolidino. Suchcompounds are, for example, as follows:

in which R, is as defined in (7) above and R is hydrogen, methyl orethyl. Such compounds are, for example:

a. 5-(4-dioxane -l,3 yl-4) benzodioxole b. 5-(4-dioxane -l ,3 yl-4)6-methyl benzodioxole c. 5-(4-dioxane -l,3 yl-4) 6-propyl benzodioxoled. 5-[(4-(5-methyl dioxane-l,3)yl] benzodioxole e. 5-[(4-(5-methyldioxane-1,3)yll] 6-propyl benzodioxole f. 5-[(4-(5-ethyl dioxane-1,3)yl] benzodioxole l2. Benzodioxole derivatives of tetraline defined byformula XII f. 5 ,6-bis( ethoxy-carbonyl) 7-methyl 5 ,6,7 ,8-

tetrahydro naphtho( 2,3-d) 1,3-dioxole g. 5 ,6-bis( propoxycarbonyl7-methyl 5 ,6 ,7 ,8-

tetrahydro naphtho(2,3-d) 1,3-dioxole h. 5,6-bis(butoxycarbonyl) 7-ethyl5,6,7,8-tetrahydronaphtho(2,3-d) 1,3-dioxole l3. Benzodioxolederivatives of dioxabicyclootane defined by formula XIII (a %;ii@;,

in which 2 and Z are the same or different and are each a direct bond oran oxygen atom; R and R are the same or different and are hydrogen,methyl or methoxy. Such, compounds are, for example:

a. 2,6-bis(5-benzodioxole-l,3 yl 3,7-dioxa bicyclo (3,3,0) octane2,6-bis(5-benzodioxole-I,3 yl oxy) 3,7-dioxa bicyclo (3,3,0) octane c.2-(5-benzodioxole-1,3 yl) 6-(5-benzodioxole-l,3

yl oxy) 3,7-dioxabicylo( 3,3,0) octane d. 2-(5-benzodioxole-1,3 yl)6-(5-(6-methoxy benzodioxole-l,3 yl)) 3,7-dioxa bicyclo(3,3,0)octane e.2-(5-benzodioxole-l,3 yl)6-(5-(6-methyl-6 benzodioxole-1,3 yl))3,7-dioxa bicyclo (3,3,0)octane 'f. 2,6-bis (5-(6-methoxybenzodioxole-1,3 yl)) 3,7-

dioxa bicyclo (3,3,0)octane g. 2,6-bis (5-(6-methyl benzodioxole-l,3yl)) 3,7-

dioxa bicyclo (3,3,0)octane 14..Benzodioxole derivatives of indoledefined by formula XIV ltm XIV

in which R,, is hydrogen, alkyl of one to four carbon atoms or alkoxy ofone to four carbon atoms, each of these groups optionally bearing agroup as defined in (10) above, R,,, is hydrogen, alkyl of one to fourcarbon atoms, alkoxy of one to four carbon atoms, alkanoyl of two tofour carbon atoms or benzoyl. Such compounds are, for example, thefollowing (1,3 dioxolo) [4,5f]indole 3-methyl (1,3 dioxolo) [4,5-f]indole 3-ethyl (1,3 dioxolo) [4,5-f] indole 3-butyl (1,3 dioxolo)[4,5-f] indole 2.3-dimethyl 1,3 dioxolo) [4,5-f]indole 3-methoxy (1,3dioxolo) [4,5-f] indole g. 3-isobutoxy (1,3 dioxolo) [4,5-f] indole h.2,3-dimethoxy (1,3 dioxolo) [4,5-f]indole i. 2-ethyl 3-methoxy (1,3dioxolo) [4,5-f]indole j. 3-(2-N,N-dimethylamino ethyl) (1,3 dioxolo)[4,5-

f] indole k. 3-(3-N-ethylamino propyl) (1,3 dioxolo) [4,5-f]

indole l. 3-(2-amino ethoxy) (1,3 dioxolo) [4,5-f]indole m.3-(2-N,N-diethylamino ethoxy) (1,3 dioxolo) [4,5-f] indole n.3-(2-pyrrolidino ethoxy) (1,3 dioxolo) [4,5-f] indole 0. 3-(2-piperidinoethoxy) (1,3 dioxolo) [4,5-f] indole p. Z-acetyl 3-(2-pyrrolidinoethoxy) (1,3 dioxolo) [4,5-f] indole q. Z-butyryl 3-(2-pyrrolidinoethoxy) (1,3 dioxolo) [4,5-f] indole r. 3-benzoyl 3-(2-pyrrolidinoethoxy) (1,3 dioxolo) [4,5-f] indole; l5. Benzodioxoles carrying animine function defined by formula XV in which R5 represents one to threesubstituents optionally chosen from alkyl of one to four carbon atoms,alkoxy of one to four carbon atoms, chloro, bromo, nitro, hydroxy andmethyl thio. Such compounds are, for example, the following anilinesN-substituted by piperonylidene a. aniline b. 4-methyl aniline c.4-butyl aniline d. 2,4-dimethyl aniline e. 4-methoxy aniline f.2,4-dimethoxy aniline g. 2,4,6-trimethoxy aniline h. 4-butoxy aniline i.3-nitr0 aniline j. S-chloro 2,4-dimethoxy aniline k. 2-chloro aniline l.2,3-dichloro aniline 4-chloro 2-methyl aniline 4-methylthio aniline2-bromo 4-nitro aniline Z-hydroxy aniline -chloro Z-methyl aniline4-bromo aniline 2,5-dichloro aniline 2,3,5-trichloro aniline2,4,6-trimethyl aniline 4-t-butyl aniline and the following anilines w.N-(3-chloro piperonylidene)-aniline x. N-(3'-methylpiperonylidene)-(4-methyl aniline) y. N-(3-nitropiperonylidene)-(3-nitro aniline);

16. Salt derivatives of benzodioxoles, having an acid or phenolicfunction defined in (3), (5) and (12) above, these salts containing ascation a metal such as sodium, potassium, calcium, zinc, cadium, copper,nickel, cobalt, iron, manganese, silver, lead, barium, strontium andaluminium, or an ammonium ion derived from ammonia, an amine derivativecontaining one to three alkyl groups and one to four carbon atoms, forexample methylamine dimethylamine, trimethylamine, diethylamine,triethylamine, butylamine, dibutylamine and tributyl amine, or aheterocyclic nitrogen derivative, e.g. pyridine, morpholine, N-methylmorpholine, piperidine and pipecolines.

Such salts are, for example, the following:

The sodium salts of compounds III (a), III (g), III (n), III (r), V (a),XII (d) and XII (e).

The ammonium salts of compounds III (a), III (h), III (m), III (p), V(i) and XII (d).

The neutral zinc salts of compounds III (a), V (a) and XII (e).

The use of these salts is of particular value when the phosphoric esterused has already undergone some protonisation; the salt introduced asstabiliser then acts as a first stage as a neutraliser for the acidphosphoric ester by exchanging its cation therewith for a proton; thisneutralisation favours the stabilisation since it has been observed bythe applicants that the preservation of phosphoric esters is better whenthey do not contain any acid by-products; the benzodioxole, having lostits cation, keeps its stabilising properties and then acts for a secondtime.

17. Salt derivatives of benzodioxoles having a basic function defined in(6) and (14) above, these salts being formed with a mineral acid such ashydrochloric, sulphuric, carbonic, boric, hydrobromic or phosphoricacid, or an organic monoor di-carboxylated acid such as acetic,propionic, benzoic, succinic, adipic, phthalic, maleic or phenylaceticacid. Such salts are, for example, the following:

(a) to (o): the chloride, sulphate, carbonate, borate,

' bromide, hydrogenphosphate, dihydrogen phosphate,

acetate, propionate, benzoate, succinate, adipate, phthalate, maleateand phenylacetate of 5-(N,N- dimethylamino )benzodioxole (VI( a) (p) to(z) and (a') to (d'): the salts ofthe same acids and in(a) to (0) justnoted of (1,3-dioxols [4,5-f] indole (XIV(a)) The solvents for thephosphoric ester may advantageously be aliphatic alicyclic or aromatichydrocar bons, which are solid or liquid at ambient temperature with-orwithout pressure. Such solvents may be used separately or in admixture.Their solvent action for the phosphoric ester and/or the henzotlioxolecan be opcompounds, ethers, esters, amides, nitriles and halogenatedhydrocarbons containing at most 12 carbon atoms. Other solvents usablein compositions according to the present invention are halogenatedhydrocarbons containing at most 12 carbon atoms, ethers and estersformed between aliphatic, cycloaliphatic or aralkoylic alcohols orphenols, and aliphatic acids or di-acids such as phthalic acid, sebacicacid or adipic acid, or even non-pesticidal phosphoric esters such asthe phosophoric tri-esters of methyl, ethyl, butyl, octyl, decyl,dodecyl, phenyl, cresyl, diphenyl, tert. butylphenyl etc. Solvents usedin the compositions according to the present invention may also be solidcompounds, for example synthetic organic resins such as homopolymers andcopolymers of vinyl derivatives (acetate, propionates, butyrate, oxides,formal, acetal, butyral, chloride etc.) and/or vinylidene or alkenederivatives (ethylene, propylene, butylene etc.) and/or styrene, and/orvinyl pyrrolidone, and/or cellulose derivatives (methyl oxide, ethyloxide, benzyl oxide, acetate, propionate, butyrate, phthalates, nitrate,etc.) and/or isoprene and/or butadiene and/or acrylic or'methacrylicesters and/or allyl esters (phthalate, isophthalate, maleate, cyanurate,etc) and also synthetic resins of the type arising from the interactionof compounds with reactive groups, as is the case with the so calledepoxy resins, formed by the condensation of an epoxide with apolyphenol, polyester resins formed by the action of a polyacid with apolyol, polyurethane resins formed by condensation of a polyisocyanatewith a polyol, or coumarone-indene type resins.

Solid compounds serving as solvents may also be natural resins, forexample colophony, shellac, tallol or a waxy resin.

Amongst mineral adjuvants which may be introduced into compositionsaccording to the present invention, the following should be noted:brick, pumice, vermiculite, kaolin, dried clay, calcium carbonate;pyrophyllite,

dolomite, glass fibre, plaster, talc, natural silica, fossil orotherwise, synthetic silica and metallic oxides. Among inert organicadjuvants which may be introduced into the compositions according to thepresent invention there should be noted: wood flour, cellulose fibre,starch, maize, faecula, sugars and/or diluents with little solventaction such as paraffin, thesev being optionally modified in theirproperties by the addition of synthetic organic resins and/or saltsfortned by alkoylamino-alkoylamines and aliphatic acids, and/or aminederivatives of montmorillonite such as bentones.

The complementary stabilisers are advantageously selected from sulphur,divalent sulphur compounds, oxiranes and azoic compounds or theirmetalliferous derivatives. Compositions according to the presentinvention can also contain one or more natural or synthetic aromaticmaterials, complementary active agents such as an acaricide, aninsectifugal agent, a birdrepellent, an antifungal agent, a vegetablegrowthregulating agent, a herbicide or a bactericide.

Thus formulated, the composition of the present invention may be solidor liquid. It can be disposed on a solid porous or fibrous support. Thissupport may be formed, for example. by a paper, a felt of wool, cottonmid/or synthetic fibre. compressed cellulose such as EXPERIMENT A 10 cmby 10 cm squares cut from a cellulose card made by the French companyFIORONI S.A. under their reference 200 were used. At the time of use,the card weighed 870 g/m i.e. 8.7 gm per square. The card squares weredivided into three groups of three units numbered A-O to A-2. Cards A-Owere impregnated with 12.5 g DDVP and the other cards were impregnatedwith 12.5 g of a solution in DDVP of one of the following compounds at aconcentration of 1%.

A-! 2-octylsulphinylpropyl) benzodioxole.

A2: 5-propyl-6-(2,5,8-trioxadodecyl) benzodioxole.

The thus impregnated squares were suspended in a room of which thetemperature was maintained at 22 i 2C, and the relative humidity ofwhich was about 40.

At the end of 15 days the quantity of DDVP destroyed by hydrolysis wasmeasured potentio metrically (it having been established elswhere thathydrolysis of DDVP in the conditions given above leads to an acidphosphoric ester and that the potentiometric measurement of the singleacidity or of the first acidity of this ester allows the quantity ofDDVP hydrolysed to be measured).

Account was taken of the acidity present in the DDVP and this wasdeducted from the results obtained.

The percentage quantities of DDVP decomposed by hydrolysis which wereformed are compiled in the table below. In the table, the valuesqualified by I represent the spread of results in each test:

EXPERIMENT B Squares of card were used as in experiment A, but of size 5.X cm and bonded in pairs, back to back, by staples, at the time of use,the card weighted 895 g/m these double cards were divided into fourgroups numbered 13-0 to B-3. Each square B-O was impregnated with 12.5 gof DDVP and the other doubled cards were each impregnated with 12.5 g ofa 1.5% solution, in DDVP, of one of the following compounds:

B-l 5-allyl benzodioxole B-2 5-formyl benzodioxole The thus impregnatedcards were suspended in a room of which the temperature was kept at 222C and of which the relative humidity was about 70.

M At the end of 15 days, the quantity of DDVP destroyed by hydrolysiswas measured as in Experiment A, the percentage quantities of DDVPdestroyed so determined are indicated in the following table.

B-O B-l B-2 EXPERIMENT C Doubled cards were used as in experiment B butin which the card weight was 885 g/m These doubled cards were dividedinto four series O0 to C-3. The doubled cards C-O were each impregnatedwith 12.5 g of DDVP, the other doubled cards being each impregnated with12.5 g of a 2% solution in DDVP of one of the following compounds:

01: 5-(3,6,9-trioxa undecyl-Z-oxy) benzodioxole tetrahydro naphtho(2,3,-d l ,3-dioxole 03: an equimolecular mixture of 2,6-bis(5-benzodioxole-1 ,3-yl)-3,7-dioxabicyclo( 3,3,0) octane and 2-(S-benzodioxole-l ,3-yl )-6-( 5benzodioxole-1,3-yl-oxy)-3,7-dioxabicyclo(3 ,3 ,0 octane The thusimpregnated cards were suspended in a room the temperature of which waskept at 22 i 2C and of which the relative humidity was about 65.

At the end of 15 days, the percentage quantity of DDVP destroyed wasmeasured as in Experiment [and is tabulated as follows:

EXPERIMENT D' Doubled cards were used as in Experiment B, but of weight890 g/m These doubled cards were divided into nine series numbered D-Oto D-8; the cards D0 were each impregnated with 12.5 g of a 30% solutionin DDVP of one of the following compounds:

D-l: S-hydroxy benzodioxole D-2: S-hydroxymethyl benzodioxole D-3:S-(propen-l yl) benzodioxole D-4: S-acetonyl benzodioxole D-5:5-(3-oxo-buten-l yl) benzodioxole D-6: 5-cyanomethyl benzodioxole D-7:5-(2-amino propyl) benzodioxole D-8: S-(S-methyl 4-dioxane-l,3 yl)benzodioxole The thus impregnated cards were suspended in a room of thetemperature of which was kept at 22 2C and the relative humidity ofwhich was between and 75.

At the end of 12 days, the percentage quantities of DDVP destroyed weremeasured as in Experiment A and tabulated as follows:

D-2 D-3 D-4 D-5 D-6 D-7 D-S 0.3 O 9.2 0.8 3.4 0 2.l i002 ii .0 $0.07 $02$0.2

5,6-bis(propyoxycarbonyl)-7-methyl-5,6,7,8-

EXPERIMENT E Doubled cards as described in Experiment B were used, butof weight 910 g/m These cards were divided into six series numbered E-Oto E5. The double cards -0 were each impregnated with 12.5 g of DDVP;the other doubled cards were each impregnated with 12.5 g of a solutionin DDVP of the following compounds in the concentrations given:

E1 2% of S-benzoylmethyl benzodioxole E2 2% of benzodioxole E3 2% ofS-bromo benzodioxole E-4 2% of S-nitrobenzodioxole E-5 5% ofS-cyanobenzodioxole.

The thus impregnated cards were suspended in a room the temperature ofwhich was kept at 22 i 2C and the relative humidity of which was about74.

At the end of days the percentage quantities of DDVP destroyed weremeasured as in Experiment A and tabulated as follows:

E0 E1 E-Z E-3 E4 E-5 EXPERIMENT F Doubled cards were used as inExperiment B but of weight 835 g/m These cards were divided into. 8series numbered F-O to F-7. Each card of E0 was impregnated with 12.5 gDDVP while the other cards were each impregnated with a 3% solution inDDVP of one F1 F2 F 3 F-4 as EXPERIMENT G Doubled cards were used asdescribed in Experiment B above but in which the weight was 910 g/mThese cards were divided into six series called G-O to G-S.

18 (3-1: sodium 7-methyl-5,6,7.,8-tetrahydronaphtho [2,3-d]1,3 dioxole5,6-dicarboxylate G-2: zinc 3(5-benzodioxole) acrylate G-3: piperidine3-(5-benzodioxole) acrylate G-4: lead 3-(5-benzodioxole) acrylate G-S:piperidine S-benzodioxole carboxylate The thus impregnated cards weresuspended in a room the temperature of which was kept at 22 2C and ofwhich the relative humidity was about 75.

I At the end of 10 days, the percentage quantities of DDVP destroyedwere measured as given in Experiment A and tabulated as follows:

EXPERIMENT H Doubled cards were used as in Experiment B but of weight910 g/m The cards were divided into three series denoted H-O, H-l, andI-I-2. The doubled cards H-O were each impregnated with 12.5 g of DDVP.

The other double cards were each impregnated with 12.5 g of a solutionin DDVP of the hydrochloride of 2benzoyl 3-(2-pyrrolidinoethoxy)1,3-dioxolo)[4,5- f]indo1e at the following concentrations:

The thus impregnated cards were suspended in a room the temperature ofwhich was kept at 22 i 2C, and of which the relative humidity was about80.

At the end of 15 days, the percentage quantities of DDVP destroyed weremeasured as noted in Experiment A and the results tabulated as follows:

The results of Experiments A, E, C, D, E, F, G and H show clearly thatwhat extent DDVP is susceptible to humidity when unprotected: they alsoshow that the hydrolysis can be reduced by a substantial amount when abenzodioxole is added to this phosphoric ester.

EXPERIMENT I 1-3 1% of 5-allyl benzodioxole 0.7% of 1-(4- methyl-Z-nitrophenylazo)-3-ethoxycarbonyl-4,4-

dimethyl-2,6-dioxo cyclohexane.

1-4 1.7% of 5-(3-oxo-butene-l yl) benzodioxole I-5 1% of 5-3-oxobutene-l yl) benzodioxole 0.7%

of l-nitro-4 methyl-2 phenylazo-3-ethoxycarbonyl-4,4-dimethy1-2,6-dioxo-cyclohexane.

The thus impregnated cards were suspended in a room the temperature ofwhich was kept at 22 t 2C,

' and of which the relative humidity was about 77.

cyclo- At the end of 21 days, the quantities of DDVP destroyed weremeasured as given in Experiment A and tabulated as follows:

EXPERIMENT J Doubled cards'were used as in Experiment B but of weight905 g/m These double cards were divided into eight series numbered J-Oto J-7. Cards J-O were each impregnated with 12.5g of DDVP, the otherdoubled cards were each impregnated with 12.5 g of a solution in DDVP asfollows:

. J-l 0.2% of elemental sulphur J-2 1.7% of 5-a1ly1 benzodioxole J-311.5% of 5-allyl benzodioxole 0.2% of elemental sulphur J-4 1.7% of5-(3-ox o butene-l yl) benzodioxole J-5 1.5% of 5-(3-oxo. butene-l yl)benzodioxole +02% of elemental sulphur.

J-6 1.7% of S-(propene-l yl) benzodioxole J-7 1.5% of 5- (propene-l yl)benzodioxole +0.27

of elemental sulphur.

The thus impregnated cards were suspended in a room the temperature ofwhich was kept at 22 i 2C and the relative humidity of which was about77.

At the end of 21 days the percentage quantities of DDVP destroyed weremeasured as given in Experiment A and tabulated as follows:

The results of this experiment show the value of mixtures of stabilisersaccording to the present invention with a complementary stabiliser suchas sulphur. There can, in effect, be seen from the results above, asynergistic effect with these two types of stabiliser.

EXPERIMENT K Doubled cards were used as in Experiment B but of size 7 X10 cm. These cards were divided into two series K-O and K-l. The doubledcards K-O were each impregnated with 16.6 g of a composition containing50% by weight DDVP and 50% by weight of a mixture of 3 parts by weightvaseline oil and 1- part by weight stearone.

The double cards K-l were each impregnated with 16.6 g of the samecomposition but in which 2.1% of the vaseline oil/stearone mixture,based on the weight of the composition, had been replaced by 2% 5-allylbenzodioxole and 0.1% of l(4-methyl-2-nitrophenylazo)-3-ethoxycarbonyl-4,4-dimethyl-2,6-dioxo cyclohexane.

The so impregnated double cards were each placed in a sachet made from apolyethylene/aluminium com- J-0 J-l J-2 J-3 J-4 v J-S .16

plex, the polyethylene face inwards, and the sachets were hermeticallysealed by welding. After 8 months storage at 40C the sachets were openedand their contents submitted to analysis as set out in Experiment A. Thepercentage quantities of DDVP decomposed were tabulated as follows:

EXPERIMENT L Four series of compositions were prepared containing 50% byweight DDVP; these series were called L-O to 13-3 The composition L-Ocontained 50% by weight xylene. The compositions L-l to L-3 containedthe following compounds, the balance to being xylene:

L-l 2% of 5-allyl benzodioxole L-2 1% of elemental sulphur L-3 12% ofS-allyl benzoidioxole and 1% of elemental sulphur.

These compositions were each enclosed in a sealed flask and placed at atemperaturev of 60C; after 36 days, the flasks were opened and theircontents analysed in the fashion described in Experiment A. Thepercentage quantities of DDVP destroyed are tabulated as follows:

The results of experiments K and L show the value of the stabilisers ofthe present invention for preserving I phosphoric esters andcompositions'containing them during storage. It also confirms the valueof associating stabilisers according to the invention with otherstabilisers.

EXPERIMENT M Cards of size 5 X 10 cm were used as in Experiment B, butleft as a single thickness. These cards were divided into four seriesM-0 to M-3. The cards M-O were each impregnated with 6g of0(2,2-dibromovinyl)-0,0- dimethyl phosphate. The other cards were eachimpregnated with 6 g of a 2% solution of one of the following compoundsin 0-(2,2-dibromovinyl)-0,0- dimethyl phosphate:

M- l 5-(3-oxo-butenl -yl) benzodioxole M-2 5-(2-aminopropyl)benzodioxole M-3 5-(3,6,9 trioxa-undecyl-2-oxy)-benzodioxole EXPERIMENTN Cards of size X cm were used as described in Experiment B, but left ata single thickness. These cards were divided into five series N-O toN-4. The Cards N-O were each impregnated with 6g of 0(2,2-dichlorovinyl)-0,0-diethyl phosphate. The other cards were eachimpregnated with 6g of a 2% solution of one of the following compoundsin 0(2,2-dichlorovinyl )0,0- diethyl phosphate.

N1 5 3-oxo-butenl -yl) benzodioxole N-2 5(2-aminopropyl) benzodioxoleN-3 5(3,6,9-trioxaundecyl-2-oxy) benzodioxole N-4 S-allyl benzodioxole.

The thus impregnated cards were suspended in a room the temperature ofwhich was kept at 22i 2C and the relative humidity of which was about60.

After 48 days, the percentage quantities of ester destroyed weremeasured as noted in Experiment A and tabulated as follows (initialacidity corresponding to 2.5% of the ester has been deducted):

sulphur compound C bam0yl)sulphide sulphur compound D bis(N,N-dimethylthiocarbamoyl)disulphide sulphur compound E thioace'tamidesulphur compound F zinc N,N-dimethyldithio carbamate sulphur compound G2-benzothiazolyl disulphide The azoic compounds used as complementarystabilisers are denoted as follows, with the exception of azobenzenewhich is referred to as such:

diazine A 1-4(phenylazo phenylazo)2-ethylamino naphthalene diazine B 1-(4-methyl-2-nitro phenylazo)-3- ethoxycarbonyl-4,4-dimethyl-2,6-dioxocyclohexane diazine C l-phenylazo-Z-naphthol diazine D l-phenylazoN,N-diethylaniline diazine E chromium complex (1:2), in admixture of thefollowing azoic compounds: l-(2-hydroxy-5-nitro phenylazo)-2-naphtholsodium salt (0.4 mole) l-(2-hydroxy-4-nitro phenylazo)-2-naphthol sodiumsalt (0.3 mole) 1-( 2-hydroxy-3-nitro-5-ter,

naphthol sodium salt (0.3 mole) In the tables in the following examples,values are expressed in weight percent throughout bisfN,N-dimethylthiocar- EXAMPLES l to 10 I Insecticidal compositionscomprising DDVP as phosphoric ester, and at least one benzodioxole asprincipal TABLEI DDVP 99.6

ocnO

dioctylphthalate dibutylsebacate diisoctyladipate lll octylepoxystearate azobenzene diazine E sulphur sulphur compound A sulphurcompound D sulphur compound G benzodioxole A benzodioxole B benzodioxoleD benzodioxole E III ISI

fill

allllllllll l"||llll||l llalllalll lg lullllll|l-ll 1H3 ill-gill|l"lll|llll llllllllll EXAMPLES ll to 20 Insecticidal compositionscomprising DDVP as phosphoric ester at least one benzodioxole asprincipal stabiliser therefor, a Vaseline or paraffin oil as solvent, aheavy alkanone as co-solvent, and in some cases a complementarystabiliser chosen from sulphur, sulphur compounds, oxiranes and azoiccompounds.

amyl-phenylazo)-2- I sulphur compound E sulphur TABLE II DDVP 50 I 50 5060 75 75 17 18 19 2O 4O 25 5O 50 Vaseline oil (a) 35 paraffin oil (a')35 35 29 l7 l7 laurone palmitone 10 stearone epoxidised soya oil diazoneB diazone C sulphur sulphur compound D sulphur compound F benzodioxole Abenzodioxole B benzodioxole C benzodioxole E LII lll

lllll (a) semi-rcfined oil having a density of 0.867 at 15C and afreezing point of about 42C. (a') semi-refined product having a densityof 0.870 at 15C and a viscosity of 1.7 Engler at 50C.

v EXAMPLES 21 to 30 Insecticidal compositions comprising DDVP aphosphoric ester, at least one benzodioxole as principal stabiliser forthis ester, a solid or semi-solid adjuvant chosen from paraffin,vaseline and petrolatum, a solvent chosen from heavy alkanones and insome cases a complementary stabiliser chosen from sulphur, sulphurcompounds, oxiranes and azoic compounds.

TABLE III zodioxole as principal stabiliser for the phosphoric ester andin some cases a complementary stabiliser 21 22 23 24 25 DDVP 15 15 20 2020 ordinary paraffin 60/62 53 53 54 ordinary paraffin 52/54 64.5 63Vaseline (b) petrolatum (b') lauronc stearonc epichlorhydrin 3 diazene Dazobenzcne sulphur compound B sulphur compound C sulphur compound (1llll bcnzodioxole A benzodioxole B benzodioxole C benzodioxole E llllllI ll lg llgl llllll Ill I'll

(b) yellow-colored technical product having a dropping point above 47C.(b!) maroon colored technical product having a dropping point of about72C.

EXAMPLES 31 to 40 5 Insecticidal compositions usable in WlCk evaporatorschosen from sulphur, sulphur compounds, oxiranes and azoic compounds.

TABLE IV DDVP 31 32 33 34 35 36 37 38 39 40 n-dodecane 86 86 86 lsoparL" (C") 85.3 84 8 6 84 86.4 84 l-chloro decane 4 6 6 3,6,9-trioxaundecane (c) 5 5 5 5 5,8,1 l-trioxa pentadecane TABLE IV Continued DDVP31 32 33 34 35 36 37 38 39 40 epoxidised soya oil 0.4 0.25 diazene A0.04 0.05 04 azobenzene 0.1 0.1 0.05 sulphur 0.03 sulphur compound A 0.10.06

benzodioxole B 0.46 ;0.8 0.1 0.1 benzodioxole C 0.25 0.27 0 Ibenzodioxole E (r) reinforcing nolvcnl known nu dlglycolilielhyl ether.and mid under the Trade Mark Diethylcarhitol" hy the 1.1.5. CompanyUnion Carbide (jimmlcaln (70. of New Vur (c) reinforcing solvent knnwnus aforementioned.

tC") distillation cut between 189 and 205C of and dodecane. sold by thecompany Esso Standard.

EXAMPLES 41 to 50 Insecticidal compositions comprising DDVP asphosphoric ester, at least one benzodioxole as principal stabilisertherefor, and odorant material chosen from linaol, ionone, methone,linalyl acetate, orange terdiglycol dibutyl ether, nold under the TradeMark Dibutylcarhitol" by the Union Carbide Chemicals Co.

branch aliphatic hydrocarbons obtained by synthesis, containing amixture ofdecane, undecane EXAMPLES 51 to 60 Insecticidal compositionscomprising DDVF as phosphoric ester, at least one benzodioxole asprincipal stabiliser, a synthetic thermoplastic resin as solid solvent,a heavy ester used as complementary solvent acting at the same time, insome cases as a plasticiser for penes and citron terpenes and in somecases a comple- 20 the resin, and in several cases as complementarystabimentary stabiliser chosen from sulphur, sulphur com-, liser chosenfrom sulphur, sulphur compounds, oxipounds, oxiranes and azoiccompounds. ranes and azoic compounds.

TABLE V I4 42 43 44 45 46 47 48 49 O DDVP 79 77 86 72 83 85 68 77 72 87linalol 7.5 a-ionone 20 5 menthone linalyl acetate 7.5 l2 orangeterpenes 30 20 citron terpenes 12 expoxidised soya oil 5 2 diazene A 0.5diazene B 0.5 sulphur 0.1 sulphur compound D 1 benzodioxole A l 1.5benzodioxole B 0.5 3 benzodioxole C 2 1.5 l benzodioxole D 1.9 2benzodioxole E 2.5 4 .2

TABLE VI 5 l 52 53 54 55 56 57 58 59 60 DDVP 20 25 20 20 25 20 25 30 30polyvinyl chloride 56 62 62 60 ethylene/vinyl acetate copolymer (d) 54.vinyl acetate/vinyl chloride copolymer (10:90) 50 54 diisooctyl adiphate23 9 tricresyl phosphate 10 29 12 19 5 methyl laurate 5 9 dioctylphthalate 9 8 l0 dimethyl succinate 15 dimethyl maleate 10 1Q octylepoxystearate 1,5 diazene C 0 2 1 sulphur 0 2 sulphur compound B 0.3 0.4sulphur compound D 0,3

benzodioxole B 1 0.2 l 6 0.41 0.9 0.5 henzodioxole C 7 0.8 l 2 0.5benzodioxole E 2.5 0,5

(d) copnlymer of 67% ethylene and 33% vinyl acetate having an intrinsicviscosity of 0.78 for 0.25 g in ml toluene at 30 (e) yellow lrgalith RAW27 28 v EXAMPLES 6l-70 l7. l,2-dibromo-2,2-dichloro propyl dimethylphos- I phate P composmons compns,mg DDVP i 18. l,2-dibromo-2,2-dichloropropyl diethyl phosphonc ester, at least one benzodioxole as principalphate stablliser therefor, a paraffin as solid ad uvant, a fossil 19.zldichloro 1 h 1 i yl dimethyl phosphate silica as mineral ad uvant,and, in some cases, a com- 20 2 z dichloro Lmeth 1 Vin l dieth l hoshate plementary stabiliser chosen from sulphur, sulphur d y h p 1compounds, oxiranes and azoic compounds, an an e cor respon m t 08p i orexam? ethylene/vinyl acetate copolymer as an agent improv- 2 Yi dlmethylthlophosphateing the mechanical properties of the paraffin, a pigment 10What (fla'lmed and/or a modified montmorillonite as dispersant ll 1. Apesticidal composition consisting essentially of: ing the composition toremain homogeneous before A. at least one phosphoric ester insecticide,the molecooling. cule of which has at least one alkyl group of one toTABLE VII 61 62 63 64 65 66 67 68 69 70 DDVP 24.25 24 24 25 25 24 24 2525 paraffin 60/62 64 65 65 57 57 57 56 52 51 68 ethylene/vinyl acetatecopolymer (71:29) l2 l2 diatomaceous earth l5 l5 l2 l2 l0 l0 l0 amineoleate (e') 5 5 modified montmorillonite 9 9 9 1 l pigment (e) 0.5 050.5 0.8 1 0.6 08

cyclohexyl epoxystearate Q- 0.7 azobenzene 1 diazene B 0.4 0.5 sulphur 1sulphur compound 8 0.2 0 4 sulphur compound F 0.3

benzodioxole A 2 l 0.5 l 2 benzodioxole B 1.3 1 benzodioxole E 0 8 0 5 a2 l (e'lproduct formed by reaction. in a molecular ratio of 2:] betweenoleic acid and a mixture of the following dinmines:

hexzldlccylaminopropylene amine l 0%) octadecylumino propylene amineoctadecylamine propylene amine (85%) (e) mixture of dimethyldihexadecylammonium montmorillonite (70%) and dimethyldioctadecylammonium n illo te It is clear that the invention is notlimited to the formulations just set forth, which are merely given asexamples of the manifold possibilities of use of the invention. Inparticular, the DDVP of these formulations can be replaced by aphosphoric ester chosen from:

2,2-dichloro vinyl dimethyl phosphate 2,2-dichloro vinyl diethylphosphate 2,2-dichloro vinyl dipropyl phosphate 2,2-dichloro vinyldibutyl phosphate 2,2,-dibromo vinyl dimethyl phosphate 2,2-dibromovinyl diethyl phosphate 2,2-dibromo vinyl dipropyl phosphate2-bromo-2chloro vinyl dimethyl phosphate 2-bromo-2-chloro vinyl diethylphosphate l0. 2,2-dichloro vinyl, ethyl methyl phosphate ll.l,2-dibromo-2,2-dichloro ethyl dimethyl phosphate l2.l,2-dibromo-2,2-dichloro ethyl diethyl phosphate 13.l-bromo-2,2,2trichloro ethyl dimethyl phosphate 14.l-bromo-2,2,2-trichloro ethyl diethyl phosphate 15. l,2,2,2-tetrabromoethyl dimethyl phosphate 16. l,2,2,2-tetrabromo ethyl diethyl phosphatethree carbon atoms attached to the phosphoric anion wherein on contactwith molecules of water, at least partial decomposition of the estertakes place by protonization replacement of said lower alkyl group byhydrogen, and I B. a 1,3-benzodioxole insecticide synergist as aprincipal agent for stabilizing the said ester against decomposition byprotonization and used in an effective stabilizing amount of from atleast about 0.2 to not more than about 10% based on the weight of thephosphoric ester, said benzodioxole having no action as a toxicitysynergist for the insecticide phosphoric acid ester in said proportions,said benzodioxole being selected from the group consisting of:5(2-octylsulphinylpropyl) benzodioxole 5 propyl-6-(2,5,8-t1ioxadodecyl)benzodioxole 5-allyl benzodioxole S-formyl benzodioxole 5-(3,6,9-trioxaundecyl-Z-oxy) benzodioxole 5,6-bis(propyoxycarbonyl)-7-methyl-5,6,7,8-

tetrahydro naphtho(2,3,-d)- l ,3-dioxole 2,6-bis( S-benzodioxole-l,3-yl)-3,7-

dioxabicyclo( 3,3,0) octane 2-( 5-.benzodioxolel ,3 ,y] )-6-(S-benzodioxolel ,3-

yl-oxy)-3,7-dioxabicyclo(3,3,0) octane S-hydroxy benzodioxoleS-hydroxymethyl benzodioxole S-(propen-l-yl) benzodioxole 5 S-acetonylbenzodioxole 5-(3-oxo-buten-1-yl) benzodioxole S-cyanomethylbenzodioxole 5-(2-amino propyl) benzodioxole 5-( 5 -methyl 4-dioxane-1,3-yl) benzodioxole S-berizoylmethyl benzodioxole benzodioxole 5-bromobenzodioxole 5-nitr0benzodioxole S-cyanobenzodioxole5(2-N-phenylcarbamyl ethyl) benzodioxole5[2-(4-methylbenzoyl)vinyl]benzodioxole 5-propyl benzodioxole5(2-nitrovinyl) benzodioxole N-piperonylidene (4-methyl aniline)N-piperonylidene (5-chloro-2,4-dimethoxy aniline)- S-methoxybenzodioxole sodium 7-methyl-5,6,7,8-tetrahydronaphtho[2,3-

2. A composition according to claim 1 ,whereinthe phosphoric esterinsecticide is 2,2-dichlorodivinyl dimethyl phosphate and thebenzodioxole is S-allyl benzodioxole.

3. A composition according to claim 1 characterised in that theproportion .of the stabilising agent is 0.5 to 6% of the weight of thephosphoric ester.

4. A composition according to claim 1 characterised in that the moleculeof the phosphoric ester contains one of two groups chosen from ethyl andmethyl groups.

5. A composition according to claim 1 characterised in that thephosphoric ester contains at least one methyl group. i

6. A composition according to claim 1 characterised in that thephosphoric ester is chosen from:

2,2-dichloro vinyl dimethyl phosphate 2,2-dichloro vinyl diethylphosphate 2,2-dichloro vinyl dipropyl phosphate 2,2-dibromo vinyldimethyl phosphate 2,2-dibromo vinyl diethyl phosphate 2,2-dibromo vinyldipropyl phosphate 2-bromo-2-chloro vinyl dimethyl phosphate2-bromo-2-chloro vinyl diethyl phosphate 2,2-dichloro vinyl, ethylmethyl. phosphate l,2-dibromo-2,2-dichloro ethyl dimethyl phosphate1,2-dibromo-2,2-dichloro ethyl diethyl phosphate l-bromo-2,2,2-trichloroethyl dimethyl phosphate l-bromo-2,2,2-trichloro ethyl diethyl phosphatel,2,2,2-tetrabromo ethyl diethyl phosphate 1,2-dibromo-2,2-dichloropropyl dimethyl phosphate l,2-dibromo-2,2-dichloro propyl diethylphosphate 2,2-dichloro l-methyl vinyl dimethyl phosphate 2,2dichlorol-methyl vinyl diethyl phosphate.

1. A PESTICIDAL COMPOSITION CONSISTING ESSENTIALLY OF: A. AT LEAST ONEPHOSPHORIC ESTER INSECTICIDE, THE MOLECULE OF WHICH HAS AT LEAST ONEALKYL GROUP OF ONE TO THREE CARBON ATOMS ATTACHED TO THE PHOSPHORICANION WHEREIN ON CONTACT WITH MOLECULES OF WATER, AT LEAST PARTIALDECOMPOSITION OF THE ESTER TAKES PLACE BY PROTONIZATION REPLACEMENT OFSAID LOWER ALKYL GROUP BY HYDROGEN, AND B. A 1,3-BENZODIOXOLEINSECTICIDE SYNERGIST AS A PRINCIPAL AGENT FOR STABILIZING THE SAIDESTER AGAINST DECOMPOSITION BY PROTONIZATION AND USED IN AN EFFECTIVESTABILIZING AMOUNT OF FROM AT LEAST ABOUT 0.2 TO NOT MORE THAN ABOUT 10%BASED ON THE WEIGHT OF THE PHOSPHORIC ESTER, SAID BENZODIOXOLE HAVING NOACTION AS A TOXICITY SYNERGIST FOR THE INSECTICIDE PHOSPHORIC ACID ESTERIN SAID PROPORTIONS, SAID BENZODIOXOLE BEING SELECTED FROM THE GROUPCONSISTING OF: 5(2-OCTYLSULPHINYLPROPYL) BENZODIOXOLE5-PROPYL-6-(2,5,8-TRIOXADODECYL) BENZODIOXOLE 5-ALLYL BENZODIOXOLE5-FORMYL BENZODIOXOLE 5-(3,6,9-TRIOXA UNDECUL-2-OXY) BENZODIOXOLE5,6-BIS(PROPYOXYCARBONYL)-7-METHYL-5,6,7,8-TETRAHYDRONAPHTHO(2,3,-D)-1,3-DIOXOLE2,6-BIS(5-BENZODIOXOLE-1,3-YL)-3,7-DIOXABICYCLO(3,3,0) OCTANE2-(5-BENZODIOXOLE-1,3,YL)-6-(5-BENZODIOXOLE-1,3-YLOXY)-3,7-DIOXABICYCLO(3,3,0) OCTANE 5-HYDROXY BENZODIOXOLE 5-HYDROXYMETHYLBENZODIOXOLE 5-(PROPEN-1-YL) BENZODIOXOLE 5-ACETONYL BENZODIOXOLE5-(3-OXO-BUTEN-1-YL) BENZODIOXOLE 5-CYANOMETHYL BENZODIOXOLE 5-(2-AMINOPROPYL) BENZODIOXOLE 5-(5-METHYL 4-DIOXANE-1,3-YL) BENZODIOXOLE5-BENZOYLMETHYL BENZODIOXOLE BENZODIOXOLE 5-BROMO BENZODIOXOLE5-NITROBENZODIOXOLE 5-CYANOBENZODIOXOLE 5(2-N-PHENYLCARBAMYL ETHYL)BENZODIOXOLE 5(2-(4-METHYLBENZOYL)VINYL)BENZODIOXOLE 5-PROPYLBENZODIOXOLE 5(2-NITROVINYL) BENZODIOXOLE N-PIPERONYLIDENE (4-METHYLANILINE) N-PIPERONYLIDENE (5-CHLORO-2,4-DIMETHOXY ANILINE) 5-METHOXYBENZODIOXOLE SODIUM 7-METHYL-5,6,7,8-TETRAHYDRONAPHTHO(2,3D)1,3DIOXOLE5,6-DICARBOXYLATE ZINE 3(5-BENZODIOXOLE) ACRYLATE PIPERIDINE3-(5-BENZODIOXOLE) ACRYLATE LEAD 3-(5-BENZODIOXOLE) ACRYLATE PIPERIDINE5-BENZODIOXOLE CARBOXYLATE 2-BENZOYL3-(2-PYRROLIDINOETHOXY)(1,3-DIOXOLO) (4,5F)INDOLE1-(4-METHYL-2-NITROPHENYL AZO)-3-ETHOXYCARBONYL-4,4DIMETHYL-1,2,6-DIOXOCYCLOHEXANE 5-ALLYL BENZODIOXOLE 5-(3-OXO-BUTENE-1-YL) BENZODIOXOLE
 2. Acomposition according to claim 1 wherein the phosphoric esterinsecticide is 2,2-dichlorodivinyl dimethyl phosphate and thebenzodioxole is 5-allyl benzodioxole.
 3. A composition according toclaim 1 characterised in that the proportion of the stabilising agent is0.5 to 6% of the weight of the phosphoric ester.
 4. A compositionaccording to claim 1 characterised in that the molecule of thephosphoric ester contains one of two groups chosen from ethyl and methylgroups.
 5. A composition according to claim 1 characterised in that thephosphoric ester contains at least one methyl group.
 6. A compositionaccording to claim 1 characterised in that the phosphoric ester ischosen from: 2,2-dichloro vinyl dimethyl phosphate 2,2-dichloro vinyldiethyl phosphate 2,2-dichloro vinyl dipropyl phosphate 2,2-dibromovinyl dimethyl phosphate 2,2-dibromo vinyl diethyl phosphate 2,2-dibromovinyl dipropyl phosphate 2-bromo-2-chloro vinyl dimethyl phosphate2-bromo-2-chloro vinyl diethyl phosphate 2,2-dichloro vinyl, ethylmethyl phosphate 1,2-dibromo-2,2-dichloro ethyl dimethyl phosphate1,2-dibromo-2,2-dichloro ethyl diethyl phosphate 1-bromo-2,2,2-trichloroethyl dimethyl phosphate 1-bromo-2,2,2-trichloro ethyl diethyl phosphate1,2,2,2-tetrabromo ethyl diethyl phosphate 1,2-dibromo-2,2-dichloropropyl dimethyl phosphate 1,2-dibromo-2,2-dichloro propyl diethylphosphate 2,2-dichloro 1-methyl vinyl dimethyl phosphate 2,2dichloro1-methyl vinyl diethyl phosphate.